JPH0542655B2 - - Google Patents

Description

[Surface developer A]

Metol 2.5g l-Ascorbic acid 10g NaBO _{2.4H 2} O 35g KBr 1g Add water 1 Furthermore, the silver halide emulsion of the present invention can be prepared by exposing the test piece prepared as described above to This provides sufficient density when developed with developer B. [Internal developer B] Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (monohydrate) 52.5g KBr 5g KI 0.5g Add water 1 To be more specific, part of the above test piece is exposed to a light intensity scale for a defined period of time up to about 1 second, and then treated with internal developer B for 20 minutes.
at least 5 times, preferably less, when developed for 4 minutes at 20°C than that obtained when another portion of the specimen exposed under the same conditions is developed in said surface developer A for 4 minutes at 20°C. Both indicate the maximum concentration of 10. Specifically, for example, the convergence silver halide emulsion described in US Pat. No. 2,592,250, the internal chemical sensitizing nuclei described in US Pat. No. 3,761,266 and US Pat. Core/shell type silver halide emulsions doped with polyvalent metal ions, JP-A-50-5824, JP-A-50-38525, JP-A-53
Loaded silver halide emulsions described in each publication of No.-2408, and other publications such as JP-A-52-156614 and the same.
Examples include the emulsion described in Japanese Patent No. 55-127549. The silver halide emulsion of the present invention can be optically sensitized using commonly used sensitizing dyes.
Combinations of sensitizing dyes used for supersensitization of internal latent sensitizing silver halide emulsions, negative-working silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, reference may be made to Research Disclosure No. 15162. The silver halide emulsion of the present invention uses commonly used stabilizers, such as compounds having an azaindene ring and a heterocycle having a mercapto ring, in order to suppress the surface sensitivity as low as possible, give a lower minimum density, and give more stable characteristics. Compounds of the formula (typically each 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene and 1-
Examples include phenyl-5-mercaptotetrazole. ) can be included. In addition, the silver halide emulsion of the present invention may contain antifoggants or stabilizers such as mercury compounds,
triazole compounds, azaindene compounds,
Benzothiazolium compounds, zinc compounds, etc. can be used. Various photographic additives may optionally be added to the silver halide emulsion of the present invention. Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylates or alkyl methacrylates and acrylic acid or methacrylics. Water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as copolymers of styrene-maleic acid, styrene-maleic anhydride-phalkyl ester copolymers, etc. are suitable. Examples of the agent include sabonin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, PH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of conditioning agents, matting agents, etc. is optional. The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to obtain an internal latent image type silver halide photographic light-sensitive material. In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent browning of dye images caused by short-wavelength actinic rays. 327, same
328 (all manufactured by Ciba Geigy) alone or in combination is advantageous. Any support can be used for the photosensitive material of the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, cellulose acetate film, and baryta film, which are subbed-treated as necessary. Includes paper, polyethylene laminate paper, etc. In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion of the present invention depending on the purpose.
Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin. In addition, in the present invention, other hydrophilic binders may be included depending on the purpose. In addition to gelatin, suitable binders include colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl-containing 19 cellulose derivatives such as cellulose acetate hydrolyzed to ~20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylamino acetate copolymers; Polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerization of proteins or saturated acylated proteins with monomers having vinyl groups,
Contains polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be used as an emulsion layer or intermediate layer, a protective layer,
It can be added to the constituent layers of the photosensitive material such as a filter layer and a backing layer depending on the purpose, and the hydrophilic binder can further contain a suitable plasticizer, lubricant, etc. depending on the purpose. Further, the constituent layers of the photosensitive material of the present invention can be hardened with any suitable hardening agent. These hardeners include chromium salts, zirconium salts,
Examples include aldehyde hardeners such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. Furthermore, in the light-sensitive material of the present invention, a large number of various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer can be coated on the support. It is possible. Specific Examples of the Present Invention The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto. Example 1 Samples ~ were prepared by sequentially applying the following layers to a resin-coated paper support from the support side. Layer 1...Cyan image-forming red-sensitive silver halide emulsion layer. An internal latent image type silver chloroiodobromide emulsion was prepared by a conversion method according to the method described in Example 1 of US Pat. No. 2,592,250. As the cyan image-forming couplers, six kinds of cyan couplers according to the present invention described below and four kinds of cyan couplers other than the present invention were used. Take 0.157 mol of each of the above cyan couplers () to (), and further mix and dissolve 2 g of 2,5-di-tert-octylhydroquinone, 100 g of dibutyl phthalate, 200 g of paraffin, and 50 g of ethyl acetate, including sodium dodecylbenzenesulfonate. Add the dispersed solution to the gelatin solution and dye it in advance. and The amount of silver is added to the emulsion spectrally sensitized by
The amount of coupler was 400 mg/m ² and the amount of coupler was 320 mg/m ² . Layer 2...Protective layer Coated so that the amount of gelatin was 200 mg/m ² . Layer 1 contained bisvinylsulfonyl methyl ether as a hardening agent and saponin as a coating aid. Samples () to () were subjected to wedge exposure using a xenon lamp, and the following [Processing 1] was performed. [Processing 1] Color development (2 minutes and 30 seconds, light fog exposure was carried out for 10 seconds after immersion in the developer) - Bleach fixing (1 minute and 30 seconds) - Water washing (1 minute and 30 seconds) - Stability (45 seconds) - Rinse (3 seconds) The processing temperature was 38°C in each step, and the composition of each processing solution was as shown below. [Color developer composition] Consists of an aqueous solution of chemicals with the following types and concentrations (g/). Potassium carbonate 28.9 Potassium sulfite 2.6 Sodium bromide 0.26 Benzyl alcohol 12.8 Ethylene glycol 3.4 Hydroxylamine sulfate 2.6 Diaminopropanol tetraacetic acid 0.09 Sodium chloride 3.2 Nitrile triacetic acid 0.4 3-Methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 4.25 PH (adjusted with potassium hydroxide) 10.20 [Bleach-fix solution composition] Consists of an aqueous solution of chemicals with the following types and concentrations (g/). Ammonium thiosulfate 110 Sodium hydrogen sulfite 10 Iron ammonium ethylenediaminetetraacetate 60 Diammonium ethylenediaminetetraacetate 5 Bisthiourea 2 PH (adjusted with aqueous ammonia) 6.5 [Stable liquid composition] Glacial acetic acid 20 Sodium acetate anhydride 5 Exposure conditions for light fog are based on the light source A daylight fluorescent lamp (Ra: 77) was used, and the illuminance was set to 1 lux on the photosensitive surface using a neutral density filter. For light fog exposure, after immersing the sample in the developer for 10 seconds,
It was taken out of the developer and placed horizontally so that the light hit the photosensitive surface vertically for 10 seconds. After exposure, it was immersed in the developer again. Also, for samples () to (), 1-phenyl-4,4-dimethyl-
150 mg of 3-pyrazolidone was added per color developer, and the color development times were 1 minute 40 seconds and 1 minute 20 seconds, respectively.
[Processing 2] and [Processing 3] were performed in the same way as [Processing 1] except that the time was changed to seconds. The minimum degree of cyan of each sample obtained by performing the above [Processing 1], [Processing 2] and "Processing 3", γ
(gamma) and cyan maximum density are shown in Table 1. The γ (gamma) value is the tangent value of the slope of the straight line connecting the two points of minimum density +0.05 and minimum density +0.30 on the characteristic curve, and is the leg γ (gamma) on the characteristic curve.
It represents.

[Table] As is clear from the results in Table 1, for samples () to () of the present invention, there was almost no decrease in γ (gamma) of the cyan legs even when treated with phenidone derivatives for a short time. A good cyan image was obtained. On the other hand, in samples () to () containing cyan couplers other than those of the present invention, when a positive image is directly formed by processing for a short time in the presence of a phenidone derivative, γ (gamma) increases and a high-contrast image occurs. Obtained. Example 2 [Processing 3] was performed using the samples of the present invention, , and samples of the present invention of Example 1, and , and the illuminance at the time of optical fog was adjusted using a neutral density filter. The same process as in Example 1 was carried out except that the lux was changed to 0.3, 0.5, 1.0, 1.5, and 2.0 lux on the photosensitive surface, respectively. The minimum and maximum densities of the cyan images of each sample obtained through the above processing are shown below.
Shown in 2.

【table】

[Table] From the results in Table 2, the samples of the present invention...
and a sample other than the present invention using a conventional cyan coupler for fluctuations in illuminance during optical fog.
, and showed stability against temperature fluctuations during optical fog. Example 3 Samples XI~ were prepared by sequentially applying the following layers onto a resin-coated paper support from the support side. Layer 1: Cyan-forming red-sensitive silver halide emulsion layer An internally latent-enhanced silver halide emulsion was prepared according to the method described in JP-A-55-127549. That is, 200 ml of a 1 molar aqueous solution of silver nitrate was quickly added at 60° C. to 220 ml of a 1 molar aqueous solution of potassium chloride containing 10 g of gelatin. After 10 minutes of physical ripening, 200 ml of a 1 molar aqueous solution of potassium bromide and 50 ml of a 0.1 molar aqueous solution of potassium iodide were added.
A mixed solution of was added. To coat the resulting compound type silver chloroiodobromide grains with a silver chloride shell, 150 ml of a 1 molar silver nitrate aqueous solution was added over 5 minutes, and after physical ripening for 20 minutes, they were washed with water. Each of the cyan couplers from XI above
Take 0.138 mole and add 2 g of 2,5-di-tert-octylhydroquinone, 50 dibutyl phthalate
g and 140 g of ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate for emulsification and dispersion. Next, the dispersion is preliminarily coated with a pigment. and In addition to the above emulsion spectrally sensitized by
Add 1 g of potassium 4-sec-octadecyl-benzenesulfonate, add bis(vinylsulfonylmethyl) ether as a hardening agent, and adjust the amount of silver.
The amount of coupler was 400 mg/m ² and the amount of coupler was 460 mg/m ² . Layer 2...Intermediate layer 100 ml of 2.5% gelatin solution containing 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutylnaphthalate.
was applied so that the amount of colloidal silver was 400 mg/m ² . Layer 3... Magenta-forming green-sensitive silver halide emulsion layer 1-(2,4,6
-trichlorophenyl)-3-(2-chloro-5
-octadecylsuccinimide anilino)-5
-Pyrazolone 40g, 2,5-di-tert-octylhydroquinone 1g, dioctyl phthalate
75 g and 30 g of ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate for emulsification and dispersion. The dispersion is then pre-dyed. and In addition to the above emulsion spectrally sensitized by
-Hydroxy-6-methyl-1,3,3a,7
- add 1 g of tetrazaindene, 1 g of potassium 2,5-dihydroxy-4-sec-octadecyl-benzenesulfonate, and add bis(vinylsulfonylmethyl) ether as a hardening agent,
Coating was carried out so that the amount of silver was 400 mg/m ² and the amount of coupler was 400 mg/m ² . Layer 4...Yellow filter layer A 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was applied so that the colloidal silver was 200 mg/ ^m2. did. Layer 5... Yellow-forming blue-sensitive silver halide agent layer α-[4-(1-benzyl-2-phenyl-3,5-dioxo-) as a yellow coupler
1,2,4-triazolidinyl)]-α-pivalyl-2-chloro-5-[γ-(2,4-di-tert
-Amylphenoxy)butylamide] 80 g of acetanilide, 1 g of 2,5-di-tert-octylhydroquinone, 80 g of dibutyl phthalate, and 200 g of ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate to emulsify and disperse. The dispersion was then added to the emulsion and 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene 1g, 2,
5-dihydroxy-4-sec-octadecyl-
Add 1 g of potassium benzenesulfonate, add bis(vinylsulfonylmethyl) ether as a hardening agent, silver amount 400 mg/m ² , coupler amount 530
It was applied at a concentration of mg/ ^m2 . Layer 6...Protective layer Coated so that the amount of gelatin was 200 mg/m ² . Note that Layer 1, Layer 2, Layer 3, Layer 4, Layer 5, and Layer 6 contained sabonin as a coating aid. For the prepared samples [Process 4] was carried out in the same manner as [Process 3] except that pyrazolidone was used. The minimum density of each dye image of yellow (Y), magenta (M) and cyan (C) of the sample obtained by the above processing, γ
(gamma), the maximum concentration was measured. These results are shown in Table 3.

【table】

[Table] As is clear from the results in Table 3, for samples XI~ of the present invention, yellow (Y), magenta
It can be seen that there is no difference in γ (gamma) values between (M) and cyan (C), and a positive image with good color balance can be obtained. On the other hand, for samples containing cyan couplers other than those of the present invention, an image with a higher γ value of the cyan image than that of the yellow (Y) and magenta (M) images is obtained. It can be seen that the color balance between Y), magenta (M), and cyan (C) is poor and the image quality deteriorates. Example 4 Using the samples used in Example 3, each sample was subjected to Treatment 1 and Treatment 2, and exposed to sunlight for 50 hours to examine the degree of fading in the portion with a standard concentration of 1.0.

[Table] In treatment 2, the residual color density after exposure to sunlight is higher than that in treatment 1.
will be lower than Although the difference is particularly large for cyan, it can be seen that the use of the cyan coupler of the present invention increases the residual color density and improves the durability against light. Example 5 Samples were prepared according to the contents shown in Table 4 according to Example 1, and evaluated according to Example 1.

[Table] As is clear from the above table, even when the samples of the present invention were treated with the phenidone derivative for a short time, there was almost no γ decrease in the cyan legs, and good images were obtained.

Claims (1)

[Scope of Claims] 1. Direct positive for forming a direct positive color image having a silver halide emulsion layer containing internal latent image type silver halide grains and cyan coupler whose grain surfaces are not fogged in advance on a support. After imagewise exposure of a silver halide color photographic light-sensitive material, prior to color development or during the color development process, direct exposure is applied to the entire surface in the presence of a phenidone derivative represented by the following general formula (). A direct positive color image forming method characterized in that the cyan coupler is represented by the following general formula () in the image forming method for obtaining a positive image. General formula () (In the formula, R ₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group.) General formula () (In the formula, R ₆ represents an alkyl group or an aryl group.
R ₇ represents an alkyl group or an aryl group. R ₈ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. J represents an imino group, n is 0 or 1
represents. Z ₁ represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. )